Method of producing mass colored beer bottles

ABSTRACT

The present invention relates to a mass colored polyester beer bottle and a method of producing a mass colored polyester beer bottle which method comprises incorporating into a polyester a dye of formula  
                 
and a UV absorber.

This is a continuation of U.S. application Ser. No. 10/492,182, pending,which is a 371 of PCT/EP02/11167 filed Oct. 4, 2002, which applicationsare hereby incorporated by reference.

The present invention relates to a method of producing coloured plasticsor coloured polymeric particles.

Dyes and the use thereof for colouring plastics and polymeric particlesare known. The use of the known dyes on their own for colouring plasticsin the mass has not, however, always fully met the increased demands,especially in terms of light fastness properties. There is accordingly aneed for new colouring methods for the production of colourations in themass that have a high tinctorial strength and, especially, lightfastness and high temperature light fastness, and that exhibit goodall-round fastness properties.

It has now, surprisingly, been found that the method according to theinvention substantially meets the above criteria.

The present invention accordingly relates to a method of producingcoloured plastics or coloured polymeric particles that comprises using adye of formula

wherein

R₁ is a radical of formula

or of formula

wherein

R₂ is hydrogen or C₁-C₄alkyl, and

R₃ is hydrogen or C₁-C₄alkyl, and/or a dye of formula

and a UV absorber.

R₂ and R₃ as C₁-C₄alkyl are each independently of the other methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

R₂ is preferably ethyl.

R₃ is preferably methyl.

For the method according to the invention, preference is given to thedyes of formulae (4),

The amounts in which the dyes are admixed with the plastics or polymericparticles to be coloured can vary within wide limits depending on thedesired depth of shade; generally, amounts of from 0.001 to 5 % byweight, especially from 0.01 to 2 % by weight, more especially from 0.03to 0.5 % by weight, based on the material to be coloured, have provedadvantageous.

UV absorbers suitable for the method according to the invention includeespecially 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones,esters of substituted or unsubstituted benzoic acid, acrylates,oxamides, 2-(2-hydroxyphenyl)-1,3,5-triazines, monobenzoates ofresorcinol and formamidines, and also a polyester UV absorber of formula

having a specific weight of from 1200 to 1400, preferably from 1300 to1350, at 25° C.

From the class of the 2-(2′-hydroxyphenyl)benzotriazoles the following,for example, may be mentioned:2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-iso-octyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the product of the esterification of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300;

wherein R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole;and2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

From the class of the 2-hydroxybenzophenones the following, for example,may be mentioned: 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-,4-dodecyloxy-, 4-benzyloxy-, 4,2′, 4′-tri-hydroxy- and2′-hydroxy-4,4′-dimethoxy derivatives.

From the class of the 2-(2-hydroxyphenyl)-1,3,5-triazines the following,for example, may be mentioned:2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyl-oxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazineand 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

From the class of the oxamides the following, for example, may bementioned: 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N, N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and a mixture thereof with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

As esters of substituted or unsubstituted benzoic acid the following,for example, may be mentioned: 4-tert-butyl-phenyl salicylate, phenylsalicylates, octylphenyl salicylates, dibenzoylresorcinol,bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

From the class of the acrylates the following, for example, may bementioned: ethyl-α-cyano-β,β-diphenyl acrylate,isooctyl-α-cyano-β,β-diphenyl acrylate, methyl-α-carbomethoxycinnamate,methyl-α-cyano-β-methyl-p-methoxycinnamate,butyl-α-cyano-β-methyl-p-methoxycinnamate,methyl-α-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyano-vinyl)-2-methylindoline.

A monobenzoate resorcinol is, for example, a compound of formula

A formamidine is, for example, a compound of formula

As UV absorbers it is also possible to use compositions comprisingactive methine compounds, for example unsubstituted or substitutedmalonate esters, as described, for example, in U.S. Pat. No. 6,207,740,WO-A-02/14418, EP-A-0 350 386, U.S. Pat. No. 4,661,566, U.S. Pat. No.4,749,772 and EP-A-0 272 692.

The amount of UV absorber can vary within a wide range; advantageouslyfrom 0.01 to 1.0 % by weight, especially from 0.02 to 0.6 % by weight,and more especially from 0.05 to 0.4 % by weight, of a UV absorber basedon the weight of the plastics or polymeric particles is used.

The compounds of formulae (1) to (9) are known and can be prepared in amanner known per se according to known methods.

The method according to the invention of producing coloured plastics orcoloured polymeric particles is carried out, for example, by admixingwith those substrates, using roll mills or mixing or grindingapparatuses, at least one dye of formula (1) and/or the dye of formula(4) and a UV absorber, the dye and the UV absorber being dissolved orfinely distributed in the high molecular weight material. The dye and UVabsorber can be added simultaneously or in succession, it being possiblefor the order in which they are added to be selected as desired.

The dyes of formulae (1) and (4) can be used either alone or,preferably, in combination with other dyes.

Preference is given to a combination of the dye of formula (4), the dyeof formula

and the dye of formula

Preference is given likewise to a combination of the dye of formula (4),the dye of formula (5), the dye of formula (10) and the dye of formula(11).

Preference is given likewise to a combination of the dye of formula (4),the dye of formula (6), the dye of formula (10) and the dye of formula(11).

The high molecular weight organic material with the admixed dye and UVabsorber is then processed according to methods known per se, such as,for example, calendering, compression moulding, extrusion, coating,spinning, pouring or injection moulding, as a result of which thecoloured material acquires its final shape.

Admixture of the dye and the UV absorber can also be effected directlybefore the actual processing step, for example by continuously metering,directly into the inlet zone of an extruder, a pulverulent dye, apulverulent UV absorber and a granulated or pulverulent high molecularweight organic material and, optionally, also other ingredients, such asadditives, the constituents being mixed in just before being processed.Generally, however, preference is given to mixing the dye and the UVabsorber into the high molecular weight organic material prior toprocessing, since more uniformly coloured substrates can be obtained.

In order to produce non-rigid mouldings or to reduce brittleness, it isfrequently desirable to incorporate so-called plasticisers into the highmolecular weight compounds prior to shaping. There may be used asplasticisers, for example, esters of phosphoric acid, phthalic acid orsebacic acid. In the method according to the invention, the plasticiserscan be incorporated into the polymers before or after the incorporationof the dye. It is also possible, in order to achieve different colourshades, to add to the high molecular weight organic materials, inaddition to a dye of formula (I) and/or the dye of formula (4), alsofurther dyes or also other colourants in any desired amounts, optionallytogether with further ingredients, e.g. fillers or siccatives.

Preference is given to the colouring of thermoplastic plastics,especially in the form of granules or mouldings, such as, for example,containers for solid or liquid substances, for example bottles,especially containers and bottles for drinks, especially beer. Preferredhigh molecular weight organic materials that can be coloured inaccordance with the invention are generally polymers having a dielectricconstant ≧2.5, especially polyesters, polycarbonate (PC), polystyrene(PS), polymethyl methacrylate (PMMA), polyamide, polyethylene,polypropylene, styrene/acrylonitrile (SAN) andacrylonitrile/butadiene/styrene (ABS).

Especially preferred are polyesters and polyamide. More especiallypreferred are linear aromatic polyesters, which can be obtained bypolycondensation of terephthalic acid and glycols, especially ethyleneglycol, or condensation products of terephthalic acid and1,4-bis(hydroxymethyl)cyclohexane, for example polyethyleneterephthalate (PET) or polybutylene terephthalate (PBTP); alsopolycarbonates, e.g. those fromα,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, or polymersbased on polyvinyl chloride and also on polyamide, for example polyamide6 or polyamide 6.6.

Preferably, the dyes of formula (1) and (4) are used to colour beerbottles made of polyethylene terephthalate (PET).

The materials mentioned hereinabove, especially those of polyesters,that have been coloured using the method according to the invention aredistinguished by level and tinctorially strong colour shades having verygood in-use fastness properties, especially a good light fastness andhigh temperature light fastness.

The invention relates also to the use of a combination of a dye offormula (1) and/or the dye of formula (4) and a UV absorber forcolouring plastics or polymeric particles.

The invention relates furthermore to the plastics coloured in the massby the methods mentioned hereinabove.

The following Examples serve to illustrate the invention. Unlessspecified otherwise, the parts are parts by weight and the percentagesare percentages by weight. The temperatures are given in degreesCelsius. The relationship between parts by weight and parts by volume isthe same as between grams and cubic centimetres.

EXAMPLE 1

1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predriedfor 4 hours at 130° C. and then homogeneously mixed in a roller rackmixing apparatus for 15 minutes, at 60 revs/min., with 0.50 g of the azodye of formula (5) and 3.00 g of a UV absorber of formula

The homogeneous mixture is extruded at a maximum temperature of 275° C.in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6heating zones, and is cooled with water, granulated in a Marke Sheergranulator and then dried for 4 hours at 130° C. in a drier (Turb EtuveTE 25, MAPAG AG, CH-3001 Bern).

Yellow-coloured polyester granules having good all-round fastnessproperties, especially very good light fastness and high temperaturelight fastness, are obtained.

EXAMPLE 2

1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predriedfor 4 hours at 130° C. and then homogeneously mixed in a roller rackmixing apparatus for 15 minutes, at 60 revs/min., with 0.45 g of the dyeof formula (6) and 0.28 g of the UV absorber of formula (12).

The homogeneous mixture is extruded at a maximum temperature of 275° C.in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6heating zones, and is cooled with water, granulated in a Marke Sheergranulator and then dried for 4 hours at 130° C. in a drier (Turb EtuveTE 25, MAPAG AG, CH-3001 Bern).

Yellow-coloured polyester granules having good all-round fastnessproperties, especially very good light fastness and high temperaturelight fastness, are obtained.

EXAMPLE 3

1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predriedfor 4 hours at 130° C. and then homogeneously mixed in a roller rackmixing apparatus for 15 minutes, at 60 revs/min., with 0.30 g of the dyeof formula (4) 0.24 g of the dye of formula (10), 0.30 g of the dye offormula (11) and 1.8 g of the UV absorber of formula (12).

The homogeneous mixture is extruded at a maximum temperature of 275°C.in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6heating zones, and is cooled with water, granulated in a Marke Sheergranulator and then dried for 4 hours at 130° C. in a drier (Turb EtuveTE 25, MAPAG AG, CH-3001 Bern).

Green-coloured polyester granules having good all-round fastnessproperties, especially very good light fastness and high temperaturelight fastness, are obtained.

1. A method of producing mass colored beer bottles which methodcomprises forming said beer bottles from mass colored polyester whichmethod comprises incorporating into said polyester a dye of formula

and a UV absorber.
 2. A method according to claim 1, wherein the UVabsorber comprises a UV absorber from the class of the2-(2′-hydroxyphenyl)benzotriazoles, of the 2-hydroxybenzophenones, ofthe esters of substituted or unsubstituted benzoic acid, of theacrylates, of the oxamides, of the 2-(2-hydroxyphenyl)-1,3,5-triazines,of the monobenzoates of resorcinol or of the formamidines, or apolyester UV absorber of formula

having a specific weight of from 1200 to 1400, preferably from 1300 to1350, at 25° C.
 3. A method according to claim 1, which comprisesincorporating in addition to the dye of formula 4, a dye of formula


4. A method according to claim 2, which comprises incorporating inaddition to the dye of formula 4, a dye of formula


5. A method according to claim 1, which comprises incorporating inaddition to the dye of formula 4, a dye of formula


6. A method according to claim 2, which comprises incorporating inaddition to the dye of formula 4, a dye of formula


7. A method according to claim 1, wherein the polyester is polyethyleneterephthalate.
 8. A mass colored polyester beer bottle comprisingpolyethylene terephthalate which polyethylene terephthalate comprises adye of formula

and a UV absorber.
 9. A mass colored polyester beer bottle according toclaim 8, wherein the UV absorber comprises a UV absorber from the classof the 2-(2′-hydroxyphenyl)benzotriazoles, of the2-hydroxybenzophenones, of the esters of substituted or unsubstitutedbenzoic acid, of the acrylates, of the oxamides, of the2-(2-hydroxyphenyl)-1,3,5-triazines, of the monobenzoates of resorcinolor of the formamidines, or a polyester UV absorber of formula

having a specific weight of from 1200 to 1400, preferably from 1300 to1350, at 25° C.
 10. A mass colored polyester beer bottle according toclaim 8, which further comprises a dye of formula


11. A mass colored polyester beer bottle according to claim 9, whichfurther comprises a dye of formula


12. A mass colored polyester beer bottle according to claim 8, whichfurther comprises a dye of formula


13. A mass colored polyester beer bottle according to claim 9, whichfurther comprises a dye of formula